Preparation, characterization, and reactivity of scandium

Organometallics , 1993, 12 (9), pp 3645–3654 .... of [TiCl2(η-fac-NCN)(O-i-Pr)], [TiCl(η-mer-NCN)(O-i-Pr)(OTf)] Containing an η-O-Bonded Triflate...
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Organometallics 1993,12, 3645-3654

3645

Preparation, Characterization, and Reactivity of Scandium Octaethylporphyrin Complexes. X-ray Crystal Structures of (OEP)ScCH3, (OEP)ScCH(SiMe3)2,(OEP)Sc(q6-C9H7),and [(OEP)Sc12(P-OH)2 John Arnold,' Caroline G. Hoffman, Denisha Y. Dawson, and Frederick J. Hollander Department of Chemistry, University of California, Berkeley, California 94720 Received April 16, 1993" The synthesis of (0EP)ScCl from Li2(0EP)(THF)2 and ScCl3(THF)3provides a useful entry into the chemistry of a wide range of (0EP)Sc derivatives. Organometallic complexes with uand ?r-bonded ligands have been isolated and fully characterized. These include (0EP)ScR species with R = Me, CH(SiMe&, CH2CMe3, (v5-C9H7),(v5-C5H5),(v5-C5H4Me),and (v5-C5Me5), three of which have been structura_lly characterized b X-ray crystallography. For [(OEP)ScMe]&H2C12: space group P1 with a = 10.088(2) b = 13.882(2) A, c = 14.813(2) A,a = 66.469(12)', p = 81.342(14)', y = 76.561(12)', V = 1845.9(5) A3, Z = 1,R = 3.99%, and R, = 5.34%. For (OEP)ScCH(SiMe3)2: space grou P21/n witha = 12.372(10) A,b = 24.194(18) A, c = 15.393(18) A,p = 112.55(7)', V = 4255(12) 3,Z = 4, R = 12.6%, and R, = 12.8%. For (OEP)Sc(v5-CgH7):space group Pbca with a = 14.899(2) A, b = 20.999(2) A,c = 23.722(3) A, V = 7421.6(26) A3, Z = 8, R = 7.44%, and R, = 5.76%. The u-alkyls react with ketones and C 0 2to produce alkoxides and acetates, respectively. Additional derivatives with R = OCMes, 0(2,4,6-Me&Hz), N(SiMe&, and triflate have also been prepared. Hydrolysis of these complexes yields the dimeric bridging hydroxide [(OEP)Sc(p-OH)] which has also been crystallographically characterized; it crystallizes in the space group Pi with a = 10.992(2) A, b = 13.179(2) A,c = 13.650(2) A, a = 59.615(16)', = 67.226(16)', y = 76.234(14)', V = 1570.6(3) A3, Z = 1,R = 3.5%, and R, = 4.2%.

1,

8:

Introduction The dimensionsof the central core of porphyrin dianions are such that metal ions of radii 0.60-0.65 A are accommodated in the plane of the N4 ring.1-3 For smaller ions, the entire ring can ruffle through an S4-type deformation to reduce the hole size. If the metal is only slightly too large, the core can expand somewhat by doming to coordinatethe ion. The vast majority of known porphyrin chemistry is based on derivatives involving late transition metals, where an in-plane geometry directs ligands to mutually trans positions, as shown.

In plane, msM = e.g. Mn, Fe

Out of plane, cisM = e.g. Sc, Zr,Nb

For much larger metals, such as those early in the transition series, however, the metal is displaced from the N4 porphyrin plane. As a result, additional ligands on the metal are constrained to be cis to one another. Compared to the latter transition metals, very little is known about

* Abstract published in Advance ACS Abstracts, August 15, 1993.

(1)Dolphin, D. The Porphyrins; Academic: New York, 1978; Vols. 1-4. (2)Buchler, J. In Porphyrins and Metalloporphyrim; Smith, K. M., Ed.; Elsevier: New York, 1975;p 159. (3)Mashiko, T.; Dolphin, D. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Ed.; Pergamon: Oxford, U.K., 1987; Chapter 21.

0276-733319312312-3645$04.00/0

the structures, properties, and reactivitiesof these unusual, electron deficient porphyrin c~mplexes.~+~ This paper describesthe synthesis and characterization of a range of scandium porphyrin complexes. Until quite recently, the list of known scandium porphyrins was quite short. Buchler's pioneering work in this area led to OEP8 derivatives with acetate, acetylacetonate, and oxo ligands.2S In 1988 Haushalter and co-workers isolated the TTP chloride complex and the p-oxo species O[(ScTPP)12and also described an unsuccessful attempt to prepare organometallic cyclopentadienyl (Cp) derivatives.1° A major drawback to studying this general class of compounds has been the lack of clean, high-yield, largescale preparative routes. Known procedures have several drawbacks, such as the necessity to use very high-boiling solvents, often followed by purification using column chromatography. The latter procedure limits the amount (4) Arnold, J.; Hoffman, C. G. J. Am. Chem. SOC.1990,112,8620.

(5)Brand, H.; Arnold, J. J. Am. Chem. SOC. 1992,114,2266. Brand, H.; Arnold, J. Organometallics, in press. (6)Arnold, J.; Johnson, S.E.; Knobler, C. B.; Hawthorne, M. F. J.Am. Chem. SOC.1992,114,3996. (7) For recent examples of early metal porphyrin derivatives see: Berezin, B. D.; Lomova, T. N. Ruse. J.Inorg. Chem. 1981,26,203. Kim, K.; Lee, W. S.; Kim, H.-J.; Cho, S.-H.; Girolami, G. S.; Gorlin, P. A.; Suslick, K. S. Inorg. Chem. 1991,30,2652and references therein. Woo, K. L.; Hays, A. J.; Jacobson, R.A.; Day, C. L. Organometallics 1991,10, 2102. Shibata, K.; Aida, T.; Inoue, S. Chem. Lett. 1992,1173. Ryu, S.; Whang, D.; Kim, J.; Yeo, W.; Kim, K. J. Chem. Soc.,Dalton Tram 1993, 205. Kim, H.-J.; Whang, D.; Kim, K.; Do, Y. Inorg. Chem. 1993,32,360. Toscano, P. J.; Brand, H.; DiMauro, P. T. Organometallics 1993,12,30. (8)Abbreviations: OEP is the dianion of 2,3,7,8,12,13,17,18-~taethylporphyrin; TPP is the dianion of meso-tetraphenylporphyrin;"P is the dianion of meso-tetra-p-tolylporphyrin. (9)Buchler, J. W. In The Porphyrim; Dolphin, D., Ed.; Academic: . . New York, 1978; Vol. 1, p 390. (10)Sewchok, M. G.; Haushalter, R. C.; Merola, J. S. Inorg. Chim. Acta 1988,144,47.

0 1993 American Chemical Society

3646 Organometallics, Val. 12,No. 9,1993

Arnold et al.

Scheme I

a

Y

Me&, ?Me3

Y

&

9

/

I f

Ag 1'

\e

Y Conditions: (a) Me2Mg in toluene; (b) Np2Mg in toluene; (c) NaCp in THF, LiCp* in THF, Li(MeCp) in THF; (d) Na(1nd) in THF; (e) TMSOTf in toluene; (0HzO in CH2C12; (g) LiOCMea in toluene; (h) LiO(MeaCsH2)in toluene; (i) NaN(TMS)2 in toluene; (j) LiCHzSiMes in toluene.

of product that may be obtained and has the additional disadvantage that it is generally not suitable for the isolation of air- and moisture-sensitive derivatives which react with commonly used support materials. In spite of the fact that large excesses of metal acetylacetonate or halide starting materials are usually employed, incomplete conversion of the free base porphyrin to the desired metalloporphyrin is not uncommon. Recent work in our group has led to the development of a new, seeminglygeneral synthetic route to out-of-plane, early metal porphyrin derivatives. Preliminary accounts describing the synthesis of scandium and zirconium OEP derivatives, based on a metathesis reaction between the porphyrin dianion (as the lithium salt11J2)and metal halides, have appeared4-6~~3 (eq 1).

+ MC1,

-

+ 2LiC1

is on organometallic scandium porphyrin complexes. Organometallic porphyrins are relatively rare; however, they have a rich and varied chemistry as described in several excellent reviews.lS20

Results and Discussion Reaction of the dilithium salt of OEP witha slight excess of ScC13(THF)3 in refluxing toluene affords high yields (>90%)of (0EP)ScCl (eq 2). The reaction is easy to carry out on large scales, and there are no detectable side reactions. The workup procedure involves a simple hot Li,(OEP)(THF),

+ ScCl,(THF), (0EP)ScCl

-+

2LICl+ 5 T H F (2)

filtration, after which the product crystallizes from the solution as analytically pure red needles that may be handled in air without deterioration. The complex is These porphyrin halide complexes are excellent starting practically insoluble in hexane or diethyl ether; however materials for the preparation of anumber of organometallic it dissolves in moderately polar solvents such as THF, and coordination complexes, demonstrating that out-ofCHzClz, and acetone to form bright red, moisture-sensitive plane metalloporphyrin geometries are quite stable platsolutions. The UV-vis spectrum shows similar features forms for a variety of ligand systems. As such, (por)MX, to those reported for other (0EP)Sc derivatives and is systems compare favorably with the more well-studied ~ n r e m a r k a b l e .As ~ ~expected, ~ the methylene protons are metallocene species Cp2MX,.lP17 In this paper, our focus diastereotopic, giving rise to a complex multiplet centered at 6 4.19 in the 'H NMR spectrum recorded in CDCl3. It (11) Arnold, J. J . Chem. SOC.,Chem. Commun. 1990, 976. (12) Arnold, J.; Daweon, D. Y.; Hoffman, C. G. J. Am. Chem. SOC. is interesting to note that despite the low formal electron 1993,115,2707. count on the metal (10 electrons) the compound shows no (13) Martin, P.C.; Arnold, J.; Bocian, D. F. J. Phys. Chem. 1993,97, 1332. tendency to form adducts with Lewis bases such as THF, (14) Collman,J.P.;Hegedue,L.S.;Norton,J.R.;Finke,R.G.Ainciples pyridine, or PMe3. and Applications of Orgonotransition Metal Chemistry; University (0EP)ScCl functions as an excellent starting material Science Books: Mill Valley, CA, 1987. (15) Cotton, F.A.; Wilkinson, G. Aduanced Inorganic Chemistry, 5th for the preparation of a wide range of organometallic and ed.; Wiley: New York, 1988. coordination compounds, as shown in Scheme I. These (16) Thompson,M.E.;Baxter,S.M.;Bulls,A.R.;Burger,B. J.;Nolan, M.C.;Santarsiero, B. D.;Shaefer, W. P.;Bercaw,J. E. J. Am. Chem. SOC. Li,(por)

(por)MCl,,

(1)

1987,109,203. (17) Cardin, D. J.; Lappert, M. F.; Raston, C. L. Chemistry of Organ0 Zirconium and Hafnium Compounds;Ellii-Horwood: Chichester, U.K., 1986.

(18) Guilard,€2.; Lecomte, C.;Kadish, K. M. Struct. Bonding 1987,64, 205. (19) Guilard, R.;Kadish, K. M. Chem. Reu. 1988,88,1121. (20) Brothers, P.J.; Collman, J. P. Acc. Chem. Res. 1986,19, 209.

Scandium Octaethylporphyrin Complexes

Organometallics, Vol. 12, No. 9,1993 3647

Table I. Crystal Data and Collection Parameters formula mol wt space group tem ("C)

K

a( )

b (A)

(4 v (A')

c

a (deg)

B

Y (deg)

Z P (cm-9 cryst dimens (mm) reflcns measd scan rate (deg min-l) 28 range (deg) scan type no. of reflcns measd no. of unique reflcns no. of reflcns no. of params

R (%I Rw GOF

(0EP)ScMe-1 S(CHzC12) C77HiooNsSCzCl6 1t40.3 P1 -1 34 10.088(2) 13.882(2) 14.813(2) 1845.9(5) 66.469( 12) 8 1.342(14) 76.561( 12) 1 4.5 0.40 X 0.45 X 0.55 +h,*k,fl 5.49 3-45 8-28 4804 4804 3993 ( I > 3UI) 439 3.99 5.34 2.09

(OEP)ScCH(SiMe& C43H63N4Sdi~ 737.1 P2dn -85 1 2.372( 10) 24.194( 18) 15.393(18) 4255(12) 90 112.55(7) 90 4 2.6 0.21 X 0.30 X 0.47 +h,+k,fl 6.70 3-45

(OEP)Sc(vS-C9H7) C4sHsiN4Sc 692.88 Pbca -95 14.899(2) 20.999(2) 23.722(3) 7421.6(26) 90 90 90 8 2.3 0.12 X 0.28 X 0.35 +h,+k,+l 5.50 3-45 8-28 5368 4828 2316 ( I > 2 ~ 1 ) 351 7.44 5.76 1.30

W

5150 5006 2979 ( I > 2 4 216 12.6 12.8 3.47

reactions occur straightforwardly on treatment of the chloride with 1 equiv of the indicated reagent, and workup procedures are very simple, affording the products as red crystals in good to high yields. All derivatives shown in Scheme I have been characterized by elemental analysis, NMR and IR spectroscopy, and in several cases, mass spectrometry and X-ray diffraction (see below). The a-alkyl complexes (OEP)ScR, where R = Me, CH(SiMe&, and CH2CMe3, are extremely air- and moisture-sensitive, as might be expected for (formally) 10electron species. As is commonly observed in alkylporphyrins, large upfield shifts were observed in the 'H NMR resonances of metal-bound alkyl groups. For example, the methyl group appears as a slightly broadened singlet at -5.0 ppm. Substitution of a tert-butyl group in place of one of the methyl hydrogens shifts the remaining two protons (still slightly broadened) to slightly lower field (6 -4.7 ppm); the tert-butyl group also gives rise to an unusually high-field resonance (6 -1.63 ppm). This trend continues similarly for the bis(trimethylsily1)methyl complex. The alkyls react extremely rapidly with unsaturated small molecules such as CO and xylyl isocyanide; however, these reactions are not simple as judged by lH NMR and we have been unable to isolate any pure products as a result. Reactions with C02 and acetone are also fast at room temperature, but in these two cases the conversions are much cleaner, leading to the known acetate and tertbutoxide derivatives, respectively (see below). Two of these a-alkyl complexes have been structurally characterized by X-ray crystallography (Table I). The geometries of (0EP)ScMe and (OEP)ScCH(SiMe& are quite similar, as shown in Figures 1-3 and Table 11. The (0EP)ScMemolecule features a scandium coordinated in a regular square pyramidal fashion with Sc-N distances of 2.151(2)-2.158(2)A and N-Sc-C angles ranging from 107.3 to 108.8'. The scandium sits atop a planar Nq ring at a distance of 0.66 A. The OEP ligand as a whole is slightly domed and ruffled, although distances and angles within the porphyrin are normal. The Sc-C bond is 2.246(3) A, and the refined C-H distances are 0.64,0.77, and 0.81A. The latter distances are very short compared

[(OEP)SC(P-OH)1z

C36H4d%OSC 594.7 Pi -118 10.992(2) 13.179(2) 11.650(2) 1570.6(3) 59.615(16) 67.226(16) 76.234( 14) 1 3.0 0.13 X 0.27 X 0.40 +h,ik,&l 5.50 3-45 8-28 4384 41 14 3359 ( I > 3UI) 380 3.5 4.2 1.654

L3 CL4

C c22

P25

q2, b 2 4

6 2 6

Figure 1. ORTEP view of (0EP)ScMe including disordered

CHzClz solvent.

d

b

Figure 2. Packing diagram for (0EP)ScMe.

to "normal" refined C-H bonds of 0.95 A. The isotropic thermal parameter for the carbon is lower than that for the Sc, and the rms amplitudes of vibration are similarly small and highly anisotropic. Suspecting the presence of some (0EP)ScClin the crystal, we analyzed a sample from the batch used for X-ray crystallography by EI-MS, which indeed confirmed this notion. Subsequently, we deter-

Arnold et al.

3648 Organometallics, Vol. 12, No. 9, 1993

(a 34

W

Figure 4. ORTEP view of (OEP)SC(T~-C~H,).

I

@ Figure 3. ORTEP view of (OEP)ScCH(SiMea)z. Table 11. Comparison of Bond Lengths and Angles in (0EP)ScMe and (OEP)ScCH(SiMe&

Sc-N(l) SoN(2) SoN(3) Sc-N(4) Soc(37) C(37)-H(1) C(37)-H(2) C(37)-H(3) N4 plane& NIl)Sc-N(2) N(2jSc-N(3j N( 3)-Sc-N( 4) N(4)Sc-N(1) N( 1)Sc-N(3) N( 1)S~-C(37) N( 2)Sc-C(37) N(3)Sc-C(37) N(4)Sc-C(37)

(0EP)ScMe (OEP)ScCH(SiMe& Bond Lengths (A) 2.15 l(2) 2.196(6) 2.152(2) 2.151(6) 2.142(6) 2.15 7(2) 2.162(6) 2.158 (2) 2.246(3) 2.243(8) 0.77(3) 0.8l(3) 0.64(3) 0.66 0.7 1 Angles (deg) 84.83(8) 82.9(21 84.33(8j s5.4(2j 84.50(8) 82.9(2) 84.69(8) 83.7(2) 144.55(8) 141.2(2) 107.6( 1) 107.0(2) 107.3(1) 110.3(3) 107.9(1) 111.8(2) 108.82(9) 108.4(3)

mined using 1HNMR spectroscopythat (0EP)ScMereacts slowly with halogenated solvents such as the CH2Cl2 used in the recrystallization. The compound reacts much faster with CHCl3, again forming (0EP)ScCl. A combination of the data above and several refinement experiments detailed in the Experimental Section lead us to believe that the apparent Sc-C bond length has been “lengthenedn by no more than 0.02 A as a result of the chloride impurity. For comparison, the Sc-C distance in Cp*2ScMe is 2.243(11) A.16 Determination of the structure of (OEP)ScCH(SiMea)z was hampered by relatively poor crystal quality that led to rather high R factors ( R = 12.6 % ;R, = 12.8% ); however, the overall molecular structure is clearly defined, as shown in Figure 3. Sc-N bond lengths are similar to those of the methyl derivative, ranging from 2.142(6) to 2.196(6) A, and the Sc is displaced from the N4 plane slightly more than in the methyl (0.71 A) perhaps due to the presence of two bulky -&Me3 groups in the former. The Sc-C bond length is 2.243(8) A, again quite close to the OEP methyl and related species. Related lanthanide OEP alkyl derivatives were recently reported by Schaverien and Orpen. Although the parent methyl species were not

isolated, a number of substituted alkyls were described, the corresponding Lu complex was structurally characterized, and the reactivities of these compounds toward 02 and water were investigatedS2l The out-of-plane, electron deficient nature of the (0EP)Sc fragment led us to investigate the formation of a-complexes. Metalloporphyrin a-complexes are rare, and most of these are limited to $-derivatives. For the majority of metalloporphyrins, it is unsurprising that these electron rich, in-plane metals are not inclined to form stable complexes with many electron, multihapto ligands. Although related TTP derivatives do not appear to be stable,lO we found that a range of cyclopentadienyl derivatives form extremely inert $komplexes on treatment of (0EP)ScClwith 1equiv of the respective Cp anion in THF. These compounds were isolated as air-stable crystals in high yields and have been fully characterized. The 75-indenylide is the only derivative sensitive to hydrolysis in solution, a result that can be ascribed to the well-known lability of indenyl ligands relative to Cp or C P * . ~Once ~ again, large upfield shifts are observed in the lH NMR spectra of coordinated ligands: for example, the Cp resonance in (OEP)Sc($-Cp) was found at 6 1.68 ppm, a value that is some 3-4 ppm upfield of Cp ligands in nonporphyrin complexes. For the related q5-indenylide complex, similar upfield shifts were observed for the three cyclopentadienyl protons. The shielding effect is lower for protons on the phenyl ring, although even these are shifted upfield some 2 ppm relative to the free ligand. The X-ray crystal structure of (OEP)Sc(v5-CgH,) consists of well-separated molecules, as shown in Figure 4 with metrical data in Table 111. Although the indene ring is bound in an v5 fashion, the side view clearly shows that the effectively planar indene ligand is tilted with respect to the porphyrin ring. It is also evident that the 95425 ring is slid slightly with respect to the scandium: the average bond length between the scandium and C(37) and C(38) is 2.504(8) A, compared to the average Sc-C bond length for C(39) and C(45) of 2.540(8) 8,and the Sc-C(40) bond length of 2.580(8) A. The average bond length between the scandium and the nitrogens of the core is 2.182(6) A. The porphyrin itself is remarkably planar showing no marked ruffling or doming. The N4 plane is quite exact with angles of the pyrrole rings to this plane ranging from 8 . 8 O to zero. The pyrrole containing N(4) is bent slightly out of the plane away from the scandium rather than (21)Schaverien, C. J.; Orpen, A. G. Inorg. Chem. 1991,30,4968. (22) Basolo, F. Polyhedron 1990, 9, 1503.

Scandium Octaethylporphyrin Complexes

Organometallics, Vol. 12, No. 9, 1993 3649

K3

Table 111. Comparison of Bond Lengths and Angles in (OEP)Sc(v5-C&) and (OEP)Sc(+-CsH5)'

Sc-N( 1) Sc-N(2) Sc-N(3) Sc-N(4) Sc-Cp centroid sc-c (37) Sc-C (38) SeC(39) Sc-C (40) Sc-c(45) N4 plane-% N( l)-Sc-N(2) N( 2)-Sc-N( 3) N(3)-Sc-N(4) N(4)-SeN(l) N(l)-Sc-N(3)

Bond Lengths (A) 2.189(6) 2.190(6) 2.180(6) 2.170(6) 2.232(6) 2.499(8) 2.508(9) 2.539(8) 2.580(8) 2.540(8) 0.78 Angles (deg) 8 1.9(3) 82.69(24) 82.86(24) 83.2( 3) 138.15(22)

c22

2.184(3) 2.195(3) 2.184(3) 2.197(3) 2.196 2.493(4) Sc-Cp(av)

32

0.80 82.1(1) 82.4( 1) 82.4(1) 82.8(1) 136.9(1)

'Data from: Arnold, J.; Hoffman, C. G. J. Am. Chem. SOC.1990, 11 2, 8620.

toward it. The scandium sits 0.78 A above the mean plane containing the four core nitrogens and is 2.233 A from the indene Cp centroid. These data may be compared to the closely related (OEP)Sc($-CbH5) structure where both the porphyrin and the Cp ring are regularly coordinated to the s c a n d i ~ m . ~ The bond distances to the individual atoms in each ligand are the same within experimental error, with the average Sc-N bond length equal to 2.190(3) A and the average Sc-C bond length equal to 2.493(4) A. The scandium is 0.80 A removed from the mean plane of the nitrogen core and 2.196 A from the mean plane of the Cp ligand. For comparison the Sc-Cp* distance in Cp*2ScMe is 2.1701(12) A.16 The porphyrin core is slightlyruffled, with two pyrrole rings tilted down with respect to the scandium and the other two rings pointed up. The angles between the pyrrole planes and the mean plane of the porphyrin are -1.7,5.6, -1.7, and 5.6". Representative derivatives with amide, aryloxide, and alkoxide ligands were also prepared and fully characterized (Scheme I). In all cases, the OEP methylene groups are diastereotopic and signals due to groups in close proximity to the ring are shifted to higher field than in the free ligand, by up to 2-3 ppm. For example, in the silylamide derivative, a singlet for the -&Me3 protons was observed at 6 -2.28 ppm compared to 6 0.072 ppm for the free amine. In the mesitoxide complex,the ortho-methyl group protons resonate some 2.5 ppm upfield from the peak due to the para-methyl group. The triflate derivative was prepared by reaction of the chloride with trimethylsilyl triflate in toluene. No doubt due to the well-known lability of the triflate group, the complex appears to be a useful precursor to other (0EP)Sc derivatives, as judged by small-scale reactions monitored by 'H NMR spectroscopy. Hydrolysis of all (0EP)ScX derivatives produces the bright red bis(p-hydroxide) dimer [(OEP)Sc(p-OH)]a. Since the solubility properties of (0EP)ScX species and the latter are quite similar, care must be taken to exclude water, as once it is formed, the hydroxide is very difficult to remove. A diagnostic 'H NMR signal integrating to one proton per OEP was observed at 6 -7.5 ppm in C6D6 (6 -7.9 ppm in CDCl3). This signal was absent in the spectrum of the deuterium labeled compound prepared by hydrolysis of (0EP)ScCl with D2O. In addition, the

Figure 5. ORTEP view of [(OEP)Sc(pOH)I2.

frequency of the meso proton resonance (6 9.43 ppm) is shifted upfield from those seen in monomeric (0EP)MX species, usually observed in the range 6 10.0-10.5 ppm; this is no doubt a result of the electronic influence of two OEP rings on each other (cf. related upfield shifts in sandwich complexes of the type (OEP)2M13$23*24). Buchler and co-workers reported the following equilibrium between the p-oxo and hydroxide species some time ag0:25 [(OEP)Sc],(p-O)

+ H2O

-

2(0EP)ScOH

We found evidence for the pox0 complex in the E1 mass spectrum where a molecular ion corresponding to [(OEP)Sc]2(p-O) ( m l e 1170)was the highest mass peak detected; evidently, dehydration of [(OEP)Sc(p-OH)]2 is facile under these conditions. Analogous Y and Lu hydroxide species with spectroscopic properties similar to those described above for [(OEP)Sc(pL-OH)12 were reported recently.21 Confirmation of the structure of the hydroxide complex was obtained by X-ray crystallography. ORTEP views are provided in Figures 5 and 6 with metrical information in Table IV. The structure was refined to an R value of 3.5% using a model which included two full-occupancy bridging oxygens;the hydroxyl hydrogens were not located. There is slight disorder in the oxygen positions with approximately 15% of each oxygen's electron density residing across the mirror plane (see supplementary material for a picture of the disorder model). As seen in Figure 6, the two OEP rings are eclipsed with a separation of 5.06 A between the N4 planes. The Sc-0-Sc bond angle was found to be 109.89(7)" with an average Sc-0 bond length of 2.078(2) A. This structure may be compared to that determined for the bent p-oxo derivative [(TTP)Scl2(p-O) which shows the average Sc-0-Sc bond angle to be llO(3)" and the average Sc-0 bond length to be 2.08(3) A. Related Mo derivatives with single pox0 ~ , ~ ~ by contrast, bridges, such as ( p - 0 )[ M O ( O ) T P P I feature, almost linear M-0-M interactions (Mo-0-Mo = 178.63(6)"). Niobium(V) TPP complexes with bridging Nb2O3 units were reported by two separate groups some time ag0.~63~7 (23) Kim,K.;Lee,W.S.;Kim,H.-J.;Cho,S.-H.;Girolami,G.S.;Gorlin,

P. A.; Suslick, K. S. Inorg. Chem. 1991,30, 2652. (24) Buchler,J. W.;DeCian, A.;Fischer,J.;Hammerschmitt,P.; Weias, R. Chem. Ber. 1991,124, 1051. (25) Buchler, J. W.; Schneehage,H. H. Z.Naturforsch.B 1973,28,433. (26) Johnson, J. F.; Scheidt, W. R. Znorg. Chem. 1978,17,1280. (27) Lecomte, C.; Protas, J.; Guilard, R.; Fliniaux, B.; Fournari, P. J. Chem. SOC.,Dalton Trans 1979, 1306.

Arnold et al.

3650 Organometallics, Vol. 12, No. 9, 1993 Table V.

Figure 6. ORTEP view of [ (OEP)Sc(pOH)]2looking down the Sc-Sc vector. Table IV. Bond Lengths and Andes in I(OEP)Sc(N-OH)lz SC-N(l) SC-N (2) Sc-N(3) Sc-N(4) N4 plansSc

Bond Lengths (A) 2.197(2) SOSC 2.195(2) SO0 SO0 2.2 16(2) 2.203(2) SOO' 0.84 sc-0'

N(l)Sc-N(2) N ( 2)Sc-N( 3) N(3)Sc-N(4) N(4)Sc-N(1) N( l)Sc-N(3)

Angles (deg) 81.75(6) sc-osc 82.26(6) Sc-O'Sc os00 81.01(6) 82.57(6) 0'Sc-O' 135.15(6)

3.404( 1) 2.084(2) 2.072(2) 2.066( 1) 1.992( 1) 109.89(7) 113.93(1) 70.11(7) 66.07(1)

Experimental Section All manipulations were carried out under dry nitrogen or argon unless stated otherwise. Glassware was oven-dried at 140 OC for at least 24 h prior to use. Literature procedures were used to prepare LiCH(SiMe3)ZB and Liz(OEP)(THF)2.11J2 Lithium alkoxides and cyclopentadienylides were isolated as base-free solids by the addition of n-BuLi to hexane solutions of the appropriate alcohol or cyclopentadiene, respectively. Dineopentylmagnesium was prepared by the literature method,29 MgMez(dioxane) was prepared similarly but was not sublimed. Other reagents were commerciallysupplied and used as received. Tetrahydrofuran (THF),diethyl ether, toluene, and hexane were predried over 4-A molecular sieves and distilled from sodium/ benzophenone under Nz. Dichloromethane was distilled from calcium hydride under Nz. All NMR solvents were treated similarly but were distilled under vacuum. Melting points were determined in sealed capillary tubes under nitrogen and are uncorrected. IR spectra were measured as Nujol mulls between KBr or CsI plates. Chemical shifts (6) for 1H NMR spectra are reported in 6 values relative to the residual proton signal of the deuterated solvent (Le. CsD8 at 6 7.15 ppm, CDCls at 6 7.24 ppm). UV-vis spectra were recorded in 0.5-cm quartz cells and are reported in the form A, in nm (log e). Elemental analyses and mass spectra (EI, 70 eV) were performed at the departmental facility of the College of Chemistry, U. C. Berkeley. (0EP)ScCI. A 250-mL single neck round-bottom Schlenk flask was charged with 1.00 g (1.45 mmol) of LiZ(OEP)(THF)z (28) Tessier-Youngs, C.; Beachley, 0. T. Znog. Synth. 1984, 24, 95. (29) Andersen, R. A.; Wilkinson, G. J.Chem. Soc.,Dalton Trans 1977, 809.

Positional Parameters for (0EP)ScMe

atom

X

Y

Z

sc c11 c12 C13 c14 N1 N2 N3 N4 c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19 c20 c21 c22 C23 C24 C25 C26 C27 C28 C29 C30 C3 1 C32 c33 c34 c35 C36 c37 C38 c39

0.23633(1) 0.30072(9) 0.1 103(1) 0.3655(3) 0.5866(3) 0.1452(2) 0.2725(2) 0.4267(2) 0.3018(2) 0.0999(3) 0.0041(3) -0.0068(3) 0.0823(3) 0.1056(3) 0.1957(3) 0.2270(3) 0.3239(3) 0.3515(3) 0.4420(3) 0.4784(3) 0.579 l(3) 0.5906(3) 0.4944( 3) 0.4734(3) 0.3869( 3) 0.3767(3) 0.2853(3) 0.2384(3) 0.1438(3) -0.0646(3) 0.0236(3) -0.0887(3) -0.0071(4) 0.1678(3) 0.2404(4) 0.3993(3) 0.5381(4) 0.6542(3) 0.7783(3) 0.6894(3) 0.8139(3) 0.4570(3) 0.5990( 3) 0.2442(3) 0.3228(3) 0.0665(2) 0.1744(3) 0.4221(9)

0.86530( 1) 0.49348(6) 0.68405(8) 0.4232(2) 0.5 17l(2) 1.0319(2) 0.9044(2) 0.7531(2) 0.8810(2) 1.0839(2) 1.1819(2) 1.1883(2) 1.0950(2) 1.0724(2) 0.9873(2) 0.9742(2) 0.8835(2) 0.8394(2) 0.7458(2) 0.7049(2) 0.6094(2) 0.6027(2) 0.6926(2) 0.7159(2) 0.8036(2) 0.8289(2) 0.9233(2) 0.9556(2) 1.0468(2) 1.2600(2) 1.3362(2) 1.2769(2) 1.3598(2) 1.05lO(2) 1.1448(2) 0.8390(2) 0.8695(3) 0.5332(2) 0.5680(2) 0.5251(2) 0.5708(2) 0.7647(2) 0.7894(2) 0.9873(2) 1.0774(2) 0.7720(2) 0.6012(2) 0.5439(6)

0.32605( 1) 0.24115(7) 0.13297(7) 0.0152(2) 0.0260(2) 0.2853( 1) 0.1696(1) 0.3352(1) 0.4509( 1) 0.3501(2) 0.3035(2) 0.2 102 (2) 0.1995(2) 0.1 138(2) 0.0976(2) 0.0043 (2) 0.0202(2) 0.1238(2) 0.1714(2) 0.2686(2) 0.3 142(2) 0.4072(2) 0.4201 (2) 0.5052(2) 0.5198(2) 0.6065(2) 0.5890(2) 0.4916(2) 0.4450(2) 0.3502(2) 0.3471 (2) 0.1303(2) 0.063 l(2) -0.0912(2) -0.1418(2) -0.0544(2) -0).0883(2) 0.2663(2) 0.1998(2) 0.481 l(2) 0.4777(2) 0.6961(2) 0.6840(2) 0.6533(2) 0.6241(2) 0.3781(2) 0.2467(2) -0.01 59(6)

(A2)

1.20(1) 4.40(2) 4.84(3) 5.57(5) 7.55(7) 1.41(5) 1.41(5) 1.43(5) 1.3 l(5) 1.27(6) 1.44(6) 1.52(6) 1.43(6) 1.54(6) 1.46(6) 1.63(6) 1.66(6) 1.53(6) 1.54(6) 1.41(6) 1.46(6) 1.45(6) 1.38(6) 1.49(6) 1.40(6) 1.39(6) 1.38(6) 1.32(6) 1.48(6) 1.62(6) 2.24(7) 2.00(6) 3.24(8) 2.03(6) 2.97(8) 2.20(7) 3.82(8) 1.88(6) 2.79(7) 1.75(6) 2.58(7) 1.80(6) 2.67(7) 1.68(6) 2.8 l(7) 0.90(5) 2.95(8) 5.0(2)*

The starred value refers to the atom that was included with isotropic thermal parameters. The thermal parameter given for anisotropically refined atoms is the isotropic equivalent thermal parameter defined as (4/3)[a28(1,1)+ b28(2,2) +cz8(3,3) +ab(cosy)B(1,2)+ac(cos8)8(1,3) + bc(cos a)8(2,3)], where (I,6, and c are real cell parameters and b(ij) are anisotropic Ps. (1

and 0.54 g (1.47 mmol) of ScCls(THF)s. Via cannula, 150 mL of toluene was transferred into the flask and the flask was fitted with a reflux condenser. The stirred mixture was refluxed for 2 h to give a homogeneous red solution. The hot solution was filtered, hexane (100 mL) was added, and the solution was cooled to -40 "C overnight. Red crystals of the mono(to1uene) solvate of (0EP)ScClwere isolated by filtration. Although this material is sufficiently pure for synthetic purposes, recrystallization from CHzClzgave analytically pure, toluene-free compound in 92% yield (0.818 g). This procedure has been scaled up by a factor of 5 without diminution in yield. Mp: 366-370 "C. I R 1312 (m), 1266 (m), 1211 (w), 1148 (vs), 1127 (vw), 1109 (m), 1056 (s), 1014 (vs), 978 (m), 959 (s), 913 (m), 872 (w), 849 (m), 745 (m), 729 (s), 713 (m), 695 (w), 668 (w), 545 (vw),465 (w) cm-l. 'H NMR: (400 MHz, CJl6,20 OC) 6 1.81(t,J = 7 Hz, 24 H, CHzCHs), 3.97 (m, 16 H, CHzCHs),10.54 ( 8 , 4 H, CH); (300 MHz, CDCls, 20 OC) b 1.96 (t, J = 7.6 Hz, 24 H, CHzCHs), 4.20 (m, 16 H, CHzCH3),10.46 (8, 4 H, CH). UV-vis (CHZClz): 337 (4.2), 406

Organometallics) Vol. 12, No. 9,1993 3651

Scandium Octaethylporphyrin Complexes Table VI. Positional Parameters for (OEP)ScCH(SiMeh atom X Y z BO (A2) sc Si1 Si2 N1 N2 N3 N4

c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19 c20 c 21 c22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 c33 c34 c35 C36 c37 C38 c39 C40 C4 1 C42 c43

0.4258(2) 0.2110(4) 0.3124(4) 0.4021 (9) 0.5808(9) 0.5305(9) 0.3527(9) 0.313( 1) 0.303( 1) 0.391(1) 0.455(1) 0.547( 1) 0.61 1(1) 0.705(1) 0.745( 1) 0.667(1) 0.687(1) 0.620(1) 0.645(1) 0.577(1) 0.508(1) 0.425( 1) 0.358(1) 0.264( 1) 0.211(1) 0.270( 1) 0.244( 1) 0.219(1) 0.102(1) 0.426( 1) 0.528(1) 0.759(1) 0.856(1) 0.85 1(1) *0.955(1) 0.739(1) 0.680(2) 0.570(1) 0.457( 1) 0.241(1) 0.148(1) 0.112(1) -0.004( 1) 0.289(1) 0.287(2) 0.053(1) 0.210( 1) 0.449(1) 0.190(1) 0.324( 1)

0.0669( 1) 0.1757(2) 0.147l(2) -0.0138(4) 0.0694(4) 0.1074(4) 0.0255(4) -0.0494(5) -0.0932(5) -0.0826(5) -0.0323(5) -0.0083(5) 0.0392(5) 0.0626(5) 0.1068(5) 0.1096(5) 0.1462(6) 0.1448(5) 0.1787(5) 0.1605(5) 0.1 150(5) 0.0848(5) 0.0435(5) O.OlSO(5) -0.0214(5) -0.01 53(5) -0.0490(5) -0.1403(6) -0.1258(7) -0.1 183(5) -0.1590(6) 0.0393(5) -0.0055(6) 0.1425(5) 0.1237(6) 0.2252(6) 0.2779(7) 0.1834( 5 ) 0.2236(6) 0.0257(5) 0.0739(6) -0.0618(6) -0.0386(6) 0.1236(5) 0.2460(7) 0.1826(6) 0.1600(6) 0.1904(6) 0.1902(6) 0.0849(6)

0.15 15(2) 0.07 17(3) 0.2846(3) 0.2069(6) 0.2784(6) 0.0874(7) 0.0 169(6) 0.1569(8) 0.2212(8) 0.3048(8) 0.2965(8) 0.3691(8) 0.3615(8) 0.4350(8) 0.3964(8) 0.3006(8) 0.2338(9) 0.1374(8) 0.067l(8) -0.0191(8) -0.0048 (8) -0.0794(8) -0.0673(8) -0.1462(8) -0.1063(8) -0).0046(8) 0.0599(8) 0.1939(9) 0.211(1) 0.3943(9) 0.394( 1) 0.5 337(8) 0.5421(9) 0.4469(9) 0.4218(9) 0.098( 1) 0.126(1) -0.1112(9) 4.150( 1) -0.2487(9) -0.286( 1) -0.1566(9) -0.162(1) 0.1646(8) 0.103(1) 0.052( 1) -O.049(1) 0.3371(9) 0.3OO( 1) 0.3643(9)

2.26(6) 3.2(1) 3jij 1.9(2)* 2.1(2)* 2.4(2)* 2.2(2)* 1.8(3)* 2.0(3)* 1.8(3)* 2.0(3)* 2.3(3)* 2.4( 3) * 1.9(3)* 2.1(3)* 2.5(3)* 3.3(3)* 2.4(3)* 2.3(3)* 2.3( 3) * 2.1(3)* 2.0(3)* 1.9(3)* 2.3(3)* 2.4(3)* 2.4(3)* 2.3(3)* 3.1 (3) * 5.1(4)* 2.7(3)* 3.9(4)* 2.4(3)* 3.9(4)* 2.8(3)* 3.6(4)* 3.8(4)* 5.2(4)* 2.6(3)* 3.8(4)* 2.5(3)* 4.5(4)* 2.8(3) * 4.3(4)* 2.5(3)* 4.9(4)* 4.7(4)* 4.1(4)* 3.6(4)* 4.0(4)* 3.6(4)*

a Starred values refer to atoms that were included with isotropicthermal parameters. The thermal parameter given for anisotropically refined atoms is the isotropic equivalent thermal parameter defined as (4/

3)[a2B(l,l) + b28(2,2) + cz8(3,3) + a b ( m y)8(1,2)

+ ac(m 8)8(1,3)

+ b c ( m a)8(2,3)] where a, b, and care real cell parameters and o ( i j ) are anisotropic j3's.

(5.4), 538 (4.1), 576 (4.2). EI-MS: 612 (M+), 597, 577. Anal. Calcd for C.&&lN4Sc: C, 70.5; H, 7.23; N, 9.14. Found: C, 70.6; H, 7.10; N, 9.04.

(0EP)ScMe. A 30-mL aliquot of toluene was added via cannula to 0.50 g (0.71 "01) of Sc(OEP)Cl(toluene) and 0.30 g (2.6 mmol) of (CH&Mg(dioxane) in a 75-mL Schlenk tube. The reaction mixture waa allowed to stir for 12 h and filtered through a Schlenk frit, and the filtrate was concentrated to 15 mL. The solution was cooled to -40 OC overnight, affording the crystalline brick-red product as a hemitoluene solvate (0.25 g, in two crops, 59%). Mp: 297 "C dec. IR: 1149 (e), 1055 (m), 1014 (81,995 (a), 844 (m), 720 (m), 697 (w). lH NMR (400 MHz, CD2Cl2, 20 OC), 6: -6.06 (br s, 3 H, CHs), 2.00 (t, J = 8 Hz, 24 H, CHaCHs),4.21 (m, 16 H, CHzCHs), 10.53 ( s , 4 H, 0.13CNMR (400 MHz, CDaC12,20 "C), 6: 18.7,20.4,27.3,129.3,143.1,146.4. UV-via(hexanes): 332 (4.7),392(5.4),534(4.5),576(4.6). Anal.

Table VII. Positional Parameters for (OEP)Sc($-C9&) atom X Y z BO (A2) Scl 0.0371( 1) -0.01 379(6) 0.37022(1) 1.74(3) N1 N2 N3 N4

c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19 c20 c 21 c22 C23 C24 C25 C26 C27 C28 C29 C30 C3 1 C32 c33 c34 c35 C36 c37 C38 c39 C40 C4 1 C42 c43 c44 c45

0.0432(4) -0).1052(4) 0.0 148(4) 0.1639(4) 0.1213(5) O.lOOS(5) 0.0118(5) -0).0233(5) -0.1 142(5) -0.1527(5) -0.2485(5) -0.2574(5) -0.1681(5) -0.1473(5) -0.0629(5) -0.0452(5) 0.0441(5) 0.0835(5) 0.1738(5) 0.2120(5) 0.3057(5) 0.3159(5) 0.2257(5) 0.2039(5) 0.168 l(5) 0.1929(6) -0.0426(5) -0.0835(6) -0.3204(5) -0.3406(6) -0.3408(5) -0.3582(5) -0.1148(6) -0.1356(6) 0.0966(6) 0.1196(6) 0.3781(5) 0.4035(6) 0.3988(6) 0.4094(6) 0.1 133(5) 0.1384(5) 0.0647(5) -0.0095( 5 ) -0.1003(6) -0.1576(5) -0.1284(5) -0.0401(6) 0.0204( 5 )

0.0833(3) 0.0 104(3) -0.0607(3) 0.0123(3) 0.1166(3) 0.1720(3) 0.1709(3) 0.1 156(3) 0.0993(4) 0.0529(3) 0.041 2(3) -0.007 9(4) -0.0264(3) -0.0728(4) -0.0899(3) -0.1391 (3) -0.1373(3) -0.0888(3) -0.0728(4) -0.0270(3) -0.0119(4) 0.0373(3) 0.0520(4) 0.1009(4) 0.221 2(4) 0.2659(4) 0.2 180(3) 0.2697(4) 0.0807(4) 0.1419(4) -0.0412(4) -0.10 12(4) -0.1844(4) -0.2357(4) -0.1806(4) -0).2436(4) -0.0501 (4) -0.1080(4) 0.0731(4) 0.1332(4) -0.0507(4) -0.0937(4) -0.1288(3) -0.1101(3) -0.128 l(4) 4.1005(4) -0.0520(4) -0.0327(4) -0.0609(3)

0.3369(2) 0.3791 (2) 0.45 lO(2) 0.4088(2) 0.3255(3) 0.2916(3) 0.2804(3) 0.3097(3) 0.3133(3) 0.3456(3) 0.3529(3) 0.3895(3) 0.4066(3) 0.4448(3) 0.4666(3) 0.508 l(3) 0.5173(3) 0.4822(3) 0.4779(3) 0.4450(3) 0.4416(3) 0.4051(3) 0.3844(3) 0.3464(3) 0.2762(3) 0.3240(4) 0.2484(3) 0.2858(3) 0.3275(3) 0.3599(4) 0.4083 (3) 0.3748(4) 0.5293(3) 0.4878(4) 0.5564(3) 0.5297(4) 0.4692(3) 0.4356(4) 0.3904(3) 0.4243(4) 0.2822(3) 0.3240(3) 0.3420(3) 0.3093(3) 0.3078(3) 0.2701(3) 0.2335(3) 0.2338(3) 0.2721 (3)

1" 1.9ii j 1.7(1) 1.9( 1) 1.9(2)* 1.6(2)* 1.8(2)* 1.7(2)* 2.0(2)* 1.5(2)* 1.9(2)* 2.1(2)* 1.8(2)* 2.0(2)* 1.8(2)* 2.0(2)* 2.0(2)* 1.7(2)* 2.2(2)* 1.8(2)* 2.4(2)* 2.0(2)* 1.8(2)* 2.1(2)* 2.8(2) 4.3(3) 2.7(2) 3.7(2) 2.6(2) 3.6(2) 2.8(2) 3.8(2) 3.1(2) 5.1(3) 3.1(2) 4.7(3) 2.9(2) 4.1(2) 2.8(2) 4.7(3) 2.3(2) 2.6(2) 2.5(2) 2.4(2) 2.8(2) 3.0(2) 3.4(2) 3.1(2) 1.9(2)

a Starredvaluesrefertoatoms thatwereincluded withisotropicthermal parameters. The thermal parameter given for anisotropically refined atoms is defined as (4/3)[a2B(1,1) + b2B(2,2) + $B(3,3) + a b ( m y)B( 1,2) + ac(m @)B(1,3) + b c ( m a)B(2,3)] where a, b, and care real cell parameters and B ( i j ) are anisotropic ps.

Calcd for Ca.aHalN4Sc: C, 76.15; H, 8.05; N, 8.77 Found C, 76.01; H, 7.99; N, 8.67. (OEP)ScCH&Me. A Schlenk tube was charged with 0.125 g (0.177 mmol) of Sc(OEP)Cl(toluene) and 0.100 g (0.44mmol) of Mg[CH2C(CH&&. Via cannula, 20 mL of toluene was added and the reaction mixture allowed to stir 4 h. The solution waa fiitered through a Schlenk frit and the fiitrate concentrated under reduced pressure to 10 mL. An equal volume of hexanes was added and the solution allowed to cool to -40 OC, affording 0.085 g (74%) of burgundy crystals. Mp: 265 "C dec. I R 1145 (s), 1053 (m), 1013 (s),954 (m), 843 (m), 724 ( 8 ) . lH NMR (400 MHz, CP,, 20 OC), 6: -4.7 (br s, 2 H, C H ~ C M ~ S-1.63 ) , (8, 9 H, -CH2CMea), 1.88 (t, J = 8 Hz, 24 H, CHzCHs), 4.06 (m, 16 H, CH~CHS), 10.63 ( ~ , H, 4 CH). '3C NMR (400 MHz, CD2C12, 20 OC), 6: 18.8, 20.3, 32.0, 100.4, 142.7, 146.6. UV-vis (hexanes): 332 (4.6), 392 (5.4), 538 (4.3))574 (4.5). Anal. Calcd for C41Hd4Sc: C, 75.89; H, 8.54; N, 8.63. Found C, 75.95; H, 8.53; N, 8.26.

Arnold et al.

3652 Organometallics, Vol. 12,No.9, 1993 Table VIII. Positional Parameters for I(OEP)Sc(rc-OH)h ~

atom sc 0 0' N1 N2 N3 N4

c1 c2 c3 c4 c5

C6 c7 C8 c9 c10

c11

c12 C13 C14 C15 C16 C17 C18 C19 c20 c21 c22 C23 C24 C25 C26 C27 C28 C29 C30 C3 1 C32 c33 c34 c35 C36

X

0.06250(4) -0.0120(2) 0.097 0.2050(2) 0.2442(2) -0).0097(2) -0,.0515(2) 0.1668(2) 0.2644(2) 0.3626(2) 0.3244(2) 0.3939(2) 0.3575(2) 0.4305(2) 0.3601(2) 0.2438(2) 0.1450(2) 0.0302(2) -0.0650(2) -0,1621(2) -0,.1267(2) -0.1982(2) -0.1635(2) -0.2367(2) -0.1673 (2) -0.0512(2) 0.0486(2) 0.2492(3) 0.1539(3) 0.4823(3) 0.4555(3) 0.5549(2) 0.5279(3) 0.3888(2) 0.3254(3) -0.0513(3) 0.0480(3) -0.2798(3) -0.2525(3) -0.3614(2) -0.3375(3) -0.1972(2) -0.1369(3) .

I

Y

z

0.05948(4) 0.0954(2) , , -0.002 0.1899(2) -0.0414(2) -0.0119(2) 0.2171(2) 0.2991(2) 0.3386(2) 0.2525(2) 0.1595(2) 0.0518(2) -0.0423(2) -0.1546(2) -0.2214(2) -0.1495(2) -0.1839(2) -0,.1201(2) -0.1580(2) -0.07 18(2) 0.0199(2) 0.1258(2) 0.2188(2) 0.3307(2) 0.397 6(2) 0.3253(2) 0.3605(2) 0.4483(2) 0.4346(2) 0.2457(2) 0.1849(2) -0.1894(2) -0).2276(2) -0.3470(2) -0.4320(2) -0.2692(2) -0.2629(2) -0).0671(2) -0.0168(2) 0.3665(2) 0.4067(2) 0.5230(2) 0.61 ll(2)

0.05480(4) -0.0793(2) -0.067 -0.0945(2) 0.0898(2) 0.2522( 1) 0.0667( 1) -0.17 1 8( 2) -0).2895(2) -0.2824(2) -0.1600(2) -0.1 15 l(2) -0.0002( 2) 0.0407(2) 0.1575(2) 0.1873(2) 0.2978(2) 0.3298(2) 0.1490(2) 0.4429(2) 0.3192(2) 0.2735(2) 0.1577(2) 0.1 159(2) -0.0008(2) -0.0306(2) -0.1405(2) -0).3991(2) -0.4468 (2) -0.3813(2) -0.4397(2) -0.0353(2) -0.1 126(2) 0.2385(2) 0.2302(2) 0.55 8 3 (2) 0.6070(2) 0.5440(2) 0.6101(2) 0.1916(2) 0.2684(2) -0.0832(2) -0.0776(2)

(A2) 1.25(1) 2.93(6) 4.0' 1.47(5) 1.5 l(5) 1.48(5) 1.50(5) 1.50(6) 1.65(6) 1.65(6) 1.47(6) 1.56(6) 1.53(6) 1.66(6) 1.57(6) 1.56(6) 1.70(6) 1.56(6) 1.74(6) 1.7 l(6) 1.60(6) 1.67(6) 1.52(6) 1.61(6) 1.57(6) 1.52(6) 1.65(6) 2.08(7) 2.85(8) 2.07(7) 3.14(8) 1.96(7) 2.48(7) 2.01(7) 2.7l(8) 2.08(7) 2.8l(8) 2.24(7) 3.41(8) 2.02(7) 2.39(7) 1.84(6) 2.33(7)

BO

a Starred values refer to atoms that were includedwith isotropicthermal parameters. The thermal parameter given for anisotropically refined atoms is the isotropic equivalent thermal parameter defined as (4/ 3)[a2B(l,l) + b2B(2,2) c2B(3,3) ab(cosy)B(1,2) + ac(cosb)B(1,3) 6c(cos a)B(2,3)] where a, 6, and care real cell parameters, and E(&*) are anisotropic j3's.

+

+

+

(OEP)ScCH(SiMe&. (0EP)ScCl (0.25 g, 0.41 mmol) and LiCH(SiMe& (0.068 g, 0.41 mmol) were combined in a 100-mL flask. Addition of toluene (20 mL) gave a dark red solution that was stirred for 20 min before being evaporated under vacuum. The residue was extracted with EhO (50 mL), and the solution was filtered, concentrated, and cooled to -40 "C overnight. The product was filtered off as dark red crystals (0.15 g, 50%, mp 237-245 OC). I R 1239 (m), 1149 (s), 1108 (m), 1057 (51,1013 (s), 957 (s),913 (m),867 (s),840 (s), 731 (m),664 (m) cm-l. EI-MS: 735 (M+ - H), 721, 577. 'H NMR (250 MHz, C&, 20 "C), 6: -5.78 (8, 1 H, CH(SiMe&), -1.84 (8, 18 H, CH(SiMe&), 1.87 (t, J = 7 Hz, 24 H, CH2CH3),4.03 (m, 16 H, CH2CH3), 10.58 ( s , 4 H, CH). UV-vis (CH2C12): 570 (4.3), 530 (4.0), 390 (5.3). Anal. Calcd for C41H49N4Sc: C, 70.1; H, 8.61; N. 7.60. Found C, 70.3; H, 8.57; N, 7.40. (OEP)Sc($-C&). Addition of THF (10 mL) to a mixture of (0EP)ScCl (0.10 g, 0.16 mmol) and LiCp (0.012 g, 0.16 mmol) gave a bright red solution that was stirred for 3 h before being evaporated under vacuum. The residue was extracted with toluene (10 mL), filtered, concentrated to ca. 2 mL, and layered with pentane (5mL). The layers were allowed to diffuse at 0 "C for 2 days. Red needles of the product (mp 312-317 "C) were isolated by filtration (0.10 g, 95%). I R 1312 (w), 1269 (m), 1147

(s),1107 (m), 1057 (s), 1009 (s), 979 (m), 957 (s), 842 (s), 741 (m), 700 (m) cm-'. EI-MS: 642 (M+),577. 1H NMR (300 MHz, 20 "C), 6: 1.68 (8, 5 H, Cp), 1.87 (t, J = 7 Hz, 24 H, CHzCHs), 4.00 (m, 16 H, CH~CHS), 10.44 (8, 4 H, CHI. UV-vis (CH2C12): 568 ( 4 . 4 , 532 (4.1), 390 (5.4). Anal. Calcd for C4lHlgN4Sc: C, 76.6; H, 7.68; N, 8.72. Found: C, 76.6; H, 7.71; N, 8.53.

(OEP)Sc($-C6Me6). Replacing Licp in the above reaction with Li(C5Me5)produced 0.11 g (96%)of bright red needles (mp 290-292 "C). I R 1690 (w), 1313 (w), 1266 (m), 1147 (81, 1109 (m), 1056 (s), 1012 (e), 978 (m), 954 (s), 843 (e), 741 (m), 699 (m) cm-l. EI-MS: 712 (M+),577. 'H NMR (300 MHz, c&, 20 "C), 6: -0.61 (8, 15 H, C5Me5),1.94 (t,J = 7 Hz, 24 H, CHZCH~), 4.00 (m, 16 H, CHZCH~), 10.44 ( s , 4 H, CHI. UV-vis (CH2C12): 568 ( 4 4 , 5 3 2 (4.1), 390 (5.4). Anal. Calcd for C I ~ H ~ ~ N C, ~ S77.5; C: H, 8.34; N, 7.86. Found: C, 77.5; H, 8.37; N, 7.73. (OEP)Sc($-C6&Me). Replacing LiCp in the above reaction with Li(C5HrMe) produced 0.085 g (81%)of bright red needles (mp 245-247 "C). I R 1314 (w), 1267 (m), 1146 (51,1055 (81,1016 (s), 956 (s), 912 (w), 843 (s), 780 (s), 746 (m), 697 (m) cm-l. 'H NMR (300 MHz, C ~ D20, ,"C), 6: -0.62 (8, 3 H, CaH&fe), 1.49 (t, J = 2 Hz, 2 H, Ca4Me), 1.57 (t, J = 2 Hz, 2 H, C&Me), 1.88 (t,J = 7 Hz, 24 H, CHZCH~), 4.03 (m, 16 H, C&CH3), 10.44 (s, 4 H, CH). UV-vis (CH2C12): 568 (4.6),532 (4.3),402(5.5). Anal. Calcd for C42HS1N4Sc:C, 76.8; H, 7.83; N, 8.54. Found: C, 76.1; H, 7.66; N, 8.34. (OEP)Sc($-COH,). A 100-mL round-bottom Schlenk flask was charged with 0.400 g (0.652 mmol) of (0EP)ScCl and 0.084 g (0.688 mmol) of LiCgH, (prepared by the deprotonation of freshly distilled indene in hexanes with n-butyllithium). Via cannula, 50 mL of toluene was transferred into the flask. The solution was allowed to stir for 15 min at room temperature, turni?g bright red. The reaction mixture was transferred to a Schlenk frit, and the LiCl was removed by filtration of the solution through the frit. The filtrate was concentrated under reduced pressure to approximately 15 mL and placed in the -40"C freezer for 48 h; 0.293 g (65%) of crystalline (OEP)Sc(+-CsH,) was obtained. Mp: 265-269 "C. IR: 1455 (vs), 1334 (m), 1312 (m), 1265 (m), 1214 (m), 1186 (w), 1146 (s), 1129 (w), 1109 (m), 1056 (vs), 1046 (m), 1013 (vs), 978 (m), 953 (vs), 912 (m), 849 (m), 842 (s), 826 (w), 803 (w), 774 (vs), 747 (m), 739 (s), 731 (s), 706 (m), 603 (w), 543 (w), 493 (w), 485 (w), 436 (s) cm-l. 'H NMR (300 MHz, CDCl3, 20 "C) 6 1.46 (br s, 3 H, H(l), H(2), H(3)), 2.00 (t, J = 7 Hz, 24 H, CH~CHB), 4.15 (m, 16 H, CHZCH~), 4.73 (m, 2 H, H(5), H(8)),5.64 (m, 2 H, H(61, H(7)),10.20 ( s , 4 H, CHI; (500 MHz, c&, 20 "C) 6 1.86 (br 8, 3 H, H(l), H(2), H(3)), 1.92 (t, J = 7 Hz, 24 H, CH2CH3),4.02 (m, 16 H, CH&H3), 5.01 (m, 2 H, H(5), H(8)), 5.82 (m, 2 H, H(6), H(7)), 10.34 ( s , 4 H, CHI. l3C NMR (400 MHz, CDC13,20 "C), 6: 18.7 (CH3), 20.0 (CHz-), 94.5 (CH),99.6 (CH),112.7 (CH),117.8 (CH), 119.1 (CH), 120.4 (CH), 142.2 (CH), 146.1 (CH). UV-vis (CH2C12): 333 (4.31, 402 (5.41, 534 (4.2), 570 (4.4). EI-MS: 692 (M+),577. Anal. Calcd for C45HS1N4Sc: C, 78.0; H, 7.42; N, 8.09. Found: C, 77.6; H, 7.43; N, 8.09. (0EP)ScOTf. Me3SiO3SCFa (160 pL,0.83 mmol) was added by syringe to 0.30 g (0.43 mmol) of Sc(OEP)Cl(toluene)in 40 mL of toluene, and the solution was allowed to stir for 6 h. The toluene was removed and the solid dried under vacuum and then extracted with a 40-mL portion of toluene. The extract was concentrated and allowed to stand at -40 "C overnight. Bright red crystals of the hemi-toluene solvate (0.21 g, 63%) were collected and dried in uucuo to remove residual solvent. Mp: 302-304 "C. I R 1318 (m), 1261 (m), 1235 (s),1188 (w), 1146 (w), 1054 (m), 1030 (m), 1012 (m), 976 (w), 950 (m), 843 (m), 730 (m), 694 (m), 623 (8). 'H NMR (300 MHz, CaD,, 20 "C), 6: 1.72 (t, J = 8 Hz, 24 H, CH2CH3),3.84 (m, 16 H, CH~CHS), 10.22 ( s , 4 H, CH). '9F{'HJ NMR (376.4 MHz, C a s , 20 "C), 6: -17.0. UVvis (hexanes): 332 (4.3), 402 (5.3), 536 (4.21, 572 (4.4). EI-MS: 726 (M+, 100%). Anal. Calcd for C ~ , ~ H ~ ~ N ~ C, O 62.94; &~SC: H, 6.26; N, 7.37. Found C, 63.36; H, 6.34; N, 7.20. (0EP)ScO'Bu. A 100-mL round-bottom Schlenk flask was charged with 0.400 g (0.652 mmol) of (0EP)ScCl and 0.052 g (0.652 mmol) of LiOC(CH&. Via cannula, 50 mL of toluene was

Scandium Octaethylporphyrin Complexes transferred into the flask. The solution was allowed to stir for 15 min at room temperature, during which time the solution became deep ruby red in color. The reaction mixture was transferred to a Schlenk frit, and the LiCl was removed by filtration of the solution through the frit. The filtrate was concentrated under reduced pressure to approximately 15 mL and placed in a -40 "C freezer overnight to yield 0.263 g (62%) of deep red crystalline (OEP)ScOC(CH3)3. Mp: 250-254 OC. IR: 1686 (w), 1576 (w), 1350 (m), 1315 (m), 1267 (m), 1203 (s), 1148 (s), 1107 (m), 1055 (s), 1013 (vs), 976 (m), 955 (s), 911 (m), 841 (s), 804 (w), 780 (m), 745 (m), 733 (s), 721 (m), 700 (m), 561 (s), 474 (w) cm-1. 1H NMR (500 MHz, CDCl3, 20 "C), 6: -1.76 (br s, 9 H, -OCMe3), 1.95 (t,J = 7 Hz, 24 H, CHZCH~), 4.19 (m, 16 H, CHzCHs),10.36 (e, 4 H, CH). UV-vis (CHzClZ): 335 (4.3),391 (5.2),404 (5.2),538 (4.1),576 (4.2). EI-MS: 650 (M+),577. Anal. Calcd for C ~ H ~ ~ N ~ O C,S73.8; C : H, 8.21; N, 8.61. Found C, 73.6; H, 8.08; N, 8.35. (OEP)ScO(2,4,6-Me&,&). Toluene (40 mL) was added to a mixture of (0EP)ScCl (0.300 g, 0.489 mmol) and Li0(2,4,6MesCeHz) (0.070g, 0.493 mmol). The solution was stirred for 15 min at room temperature, during which time the solution became deep ruby red. Filtration, concentration under reduced pressure to approximately 10mL, and cooling to -40 O C overnight afforded 0.227 g of red crystalline (OEP)Sc0(2,4,6-Me3CeH~)(65%). Mp: 295-296 "C. I R 1683 (w), 1607 (w), 1525 (vw),1319 (vs), 1273 (vs), 1212 (m), 1157 (m), 1148 (s), 1108 (m), 1062 (m), 1052 (s), 1013 (s), 975 (m), 956 (s), 910 (m), 865 (s), 851 (s), 840 (s), 804 (m), 735 (s), 702 (m), 562 (s), 496 (w), 465 (w) cm-l. lH NMR (500 MHz, CDC13,20 OC),6: -1.02 (br s,6 H,-0(2,4,6-Me3CsHz)), 1.46 (s,3H, -0(2,4,6-Me3ceHz)),1.98 (t,J=7 Hz, 24H, CHzCHs), 4.20 (m, 16 H, CHzCHs), 5.49 (8, 2 H, -0(2,4,6-Me3C&z)), 10.43 (s,4 H, CH). UV-vis (CH2Clz): 336 (4.1),399 (5.5),534 (4.0),570 (4.2). EI-MS: 712 (M+),577. Anal. Calcd for C ~ ~ H M N ~ OC, SC: 75.8; H, 7.78; N, 7.86. Found C, 75.7; H, 7.85; N, 7.53. (OEP)ScN(SiMe&. The method used to prepare the mesitoxide above was followed using 0.400 g (0.652 mmol) of (0EP)ScCl and 0.114 g (0.681 mmol) of LiN(SiMe3)z. Deep red crystalline (OEP)ScN(SiMes)zwas obtained in 58.6% yield (0.282 g). Mp: 280-285 "C. 'H NMR. (300 MHz, C&, 20 "C) 6 -1.82 (s, 18 H, -SiMe3), 1.88 (t, J = 7 Hz, 24 H, CHzCHa), 3.98 (m, 16 H, CHzCH,), 10.46 ( ~ , H, 4 CH); (300 MHz, CDCl3,20 "C) 6 -2.28 (8, 18 H, -SiMe3), 1.94 (t,J = 7 Hz, 24 H, CHZCH~), 4.13 (m, 16 H, CHzCH3),10.30 (s,4 H, CH). UV-vis (CH&12): 335 (4.2),400 (5.4), 534 (4.1), 572 (4.3). EI-MS: 737 (M+), 722, 577. Anal. Calcd for C42HezN&Siz: C, 68.3; H, 8.47; N, 9.49. Found: C, 67.9; H, 8.47; N, 9.41. [(OEP)Sc(pOH)]2. A 100-mL round-bottom Schlenk flask was charged with 0.100 g (0.162 mmol) of (0EP)ScCl and 0.027 g (0.162 mmol) of LiN(SiMe3)z. Via cannula, 20 mL of toluene was transfered into the flask. The solution was allowed to stir for 20 min at room temperature, turning deep wine red. A 100pL aliquot of degassed HzO was added by syringe. The toluene was evaporated, and the residue was extracted with CHzClz (50 mL) and filtered. Concentration, followed by cooling to -40 OC overnight, gave dark red crystals of the product as a methylene chloride solvate in 85% yield. Mp: 410-420 "C. I R 1318 (w), 1266 (m), 1212 (w), 1146 (s), 1109 (m), 1057 (s), 1013 (vs), 978 (m),954 (vs), 911 (w), 839 (vs), 802 (w), 748 (s), 718 (51,701 (m), 668 (vw), 578 (vw), 512 (m), 465 (w), 419 (w) cm-l. lH NMR (500 MHz, C& 20 "C) 6 -7.52 (8, 1H, -OH),1.67 (t,J = 7 Hz, 24 H, CHZCH~), 3.85 (m, 16 H, CH~CHS), 9.55 (s,4 H, CH); (500 MHz, CDC13, 20 OC) 6 -7.93 (9, 1 H, -OH),1.64 (t,J = 7 Hz, 24 H, CHzCH3),3.94 (m, 16 H, CHZCH~), 9.43 (s,4 H, CH). UV-vis (CHzClz): 335 (4.6),404 (5.7), 536 (4.4),574 (4.6). EI-MS: 1170 (M+),596,577. Anal. Calcd for C,~H&~ZN~OZSCZ: C, 78.8; H, 7.28; N, 8.79. Found: C, 69.0; H, 7.50; N, 8.66. X-ray Crystallography. Table I lists a summary of crystallographic data for all four structurally characterized compounds. General operating procedures (instrumentation, computation, etc.) were as previously described.m Crystals were (30) Bonasia, P. J.; Arnold, J. Inorg. Chem. 1992,31, 2508.

Organometallics, Vol. 12, No. 9, 1993 3653 covered with a layer of Paratone-N hydrocarbon oil, removed from the drybox, inspected, and mounted on glass fibers as described by H0pe.3~Mo K a radiation (A = 0.710 73 A) was used throughout. The structures were determined at the CHEXRAY facility, University of California, Berkeley. The structure of the hydroxide was determined by P. J. Bonasia and Tim Patten under the supervision of Dr. Hollander. All ORTEP views show ellipsoids scaled to the 50% probability level. (0EP)ScMe. Automatic peak search and indexingprocedures yielded a triclinic reduced primitive cell. The 4804 unique raw intensity data were converted to structure factor amplitudes and their esd's by correction for scan speed, background, and Lorentz and polarization effects. The data were corrected for a 6% intensity decay. The choice of the centric space group was confirmed by the successful solution and refinement of the structure. The structure was solved by direct methods (SHEIXS) and refined by standard least-squares and Fourier techniques. In a difference Fourier map calculated following refinement of all non-hydrogen atoms with anisotropic thermal parameters, peaks were found corresponding to the positions of all the hydrogens except those on the disordered dichloromethane molecule. Most of the hydrogens were assigned idealized locations and were not refined; however, hydrogens on the metal-bonded methyl were refined with a common thermal parameter for all three. Inspection of the residuals ordered in ranges of (sin @/A, \Fol,and parity and value of the individual indexes showed no unusual features or trends. The largest peak in the final difference Fourier map had an electron density of 0.74 e/A3 and the lowest excursion -0.09 e/A3. The largest peak was located near the chlorine5 of the dichloromethane. Two experiments were carried out following final refinement in attempts to gauge the effect of the presence of (0EP)ScCl in the crystal. In the first, the position of the methyl carbon was artificially moved inward to see what the effect on the C-H distances and Sc-C-H and H-C-H angles would be. This was based on the assumption that the overlapping Sc-C and S c C l positions would result in a lengthening of the apparent Sc-C distance. However, any movement of the carbon position sufficient to result in reasonable C-H distances also resulted in highly unreasonable Sc-C-H angles. In the second experiment, a fractional-occupancy C1 atom was constrained to the same position as the C atom with a fixed B h of 1.5 Az. With a C1 occupancy of 0.1, the thermal parameters for C37 were large and the hydrogens refined to large C-H distances. At 0.05 chlorine occupancy, the B, for the carbon was 1.9 AZ with reasonable C-H distances. The Sc-C distance did not change significantly (2.250 A). Changes in R values in both experiments were small. (OEP)ScCH(SiMe&. Automatic peak search and indexing procedures yielded a monoclinic reduced primitive cell. Inspection of the Niggli values revealed no conventional cell of higher symmetry. The 5006 unique raw intensity data were converted to structure factor amplitudes and their esd's by correction for scan speed, background, and Lorentz and polarization effects. No absorption correction was applied. The structure was solved by direct methods (SHELXS) and refined by standard leastsquares and Fourier techniques. In a difference Fourier map calculated following refinement of all non-hydrogen atoms with anisotropic thermal parameters, peaks were found corresponding to most of the positions of the hydrogens. Hydrogen atoms were assigned idealized locations and values of Bi,approximately 1.25 times the B, of the atoms to which they were bonded. They were included in the structure factor calculations,but not refined. Inspection of the residuals ordered in ranges of (sin @/A, pol, and parity and value of the individual indexes showed no unusual features or trends. (OEP)Sc(+-CoH,). Automatic peak search and indexing procedures yielded an orthorhombic reduced primitive cell. Inspection of the Niggli values revealed no conventional cell of (31) Hope, H. In Experimental OrganometalZic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; ACS Symposium Series 367; American Chemical Society: Washington, DC, 1987; p 257.

3654 Organometallics, Vol. 12, No. 9,1993 higher symmetry. The 5368 raw intensity data were converted to structure factor amplitudes and their esd’s by correction for scan speed, background, and Lorentz and polarization effects. The structure was solved by direct methods (SHELXS) and refined by standard least-squares and Fourier techniques. Hydrogens were located and treated as above;they were included in the structure factor calculations, but not refined. Inspection of the residuals ordered in ranges of (sin @/A, pol, and parity and value of the individual indexes showed no unusual features or trends. There was no indication of secondary extinction in the high-intensity low-angle data. [(OEP)Sc(p-OH)]t. The unit cell was determined to be primitive triclinic with space group Pi. The 4384 raw intensity data were converted to structure factor amplitudes and their esd’s by correction for scan speed, background, and Lorentz and polarization effects. The structure was solved by Patterson methods and refined by standard least-squares and Fourier techniques. The final residuals for 380 variables refined against the 3359 accepted data for which F > 3 a ( F ) were R = 0.035, R, = 0.042, and GOF = 1.654. Hydrogens were located and treated as above; they were included in the structure factor calculations, but not refined. Inspection of the residuals ordered in ranges of

Arnold et al. (sin @/A, pol,and parity and value of the individual indexes showed no unusual features or trends.

Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, and the Exxon Education Foundation for support of this research. We thank the Department of Education and the National Physical Sciences Consortium for fellowships (toC.G.H. and D.Y.D., respectively) and we are grateful to Phil Bonasia and Tim Patten for determining the crystal structure of the hydroxide complex. Supplementary Material Available: Tables of temperature factor expressions, positional parameters, intramolecular distances and angles, torsion angles, least-squares planes, and anisotropic thermal parameters and a figure showing a view of the disorder in [(OEP)Sc]2(pOH)2 (30 pages). Ordering information is given on any current masthead page. OM930247N